CN1842572A - Flame retardant polymer composition comprising fine particles - Google Patents
Flame retardant polymer composition comprising fine particles Download PDFInfo
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- CN1842572A CN1842572A CNA2004800244316A CN200480024431A CN1842572A CN 1842572 A CN1842572 A CN 1842572A CN A2004800244316 A CNA2004800244316 A CN A2004800244316A CN 200480024431 A CN200480024431 A CN 200480024431A CN 1842572 A CN1842572 A CN 1842572A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
The present invention relates to a flame retardant polymer composition comprising (A) an olefin homo- and/or copolymer in an amount of from 30 to 70 wt.-% of the total polymer composition, (B) a silicone-group containing compound, (C) an inorganic filler in an amount of at least 10wt% of the total polymer composition, wherein component (C) has a particle size distribution so that at least 10 wt% of the total polymer composition are particles with a size of below 0.7 micrometers. Furthermore, the invention relates to the use of such a composition in a conduit, plug, wire or cable or for injection moulding, and to a wire or cable having a layer comprising such a composition.
Description
The present invention relates to fire-retardant polymer composition, more specifically relate to a kind of flame retardant compositions that is used for electric wire or cable, said composition is when keeping for example good extrudable property of other performance, demonstrate improved flame retardant properties, perhaps between snappiness and rigidity, show good balance.In addition, the present invention relates to this fire-retardant polymer composition is used for producing the flame-retardant layer of electric wire or cable, and relate to electric wire or the cable that comprises fire-retardant combination of the present invention.
Polyolefine is congenital to be inflammable material.But, in many application, require fire-retardant, electric wire or the cable in electronics and the electrical industry for example.Known polyolefin polymer for the flame retardant resistance that is improved adds specific additive in this polymkeric substance, for example based on the pharmaceutical chemicals of halogen, based on phosphatic pharmaceutical chemicals or inorganic hydroxide/hydrate.In these additives each all has the deficiency of himself, for example with polyolefinic uncompatibility, the bad mechanical property and the bad processing characteristics that need high heap(ed) capacity level to be caused exist and give out harmful, poisonous or other unwelcome compound and expense height.
For instance, as described in EP 0 393 959 or the WO 9812253, a kind of flame retardant compositions can comprise a kind of silica-based compound that contains, the mineral filler of the also non-hydrate in fact of a kind of both non-hydroxides and a kind of organic polymer matrix that typically contains a kind of acrylate and acetic ester.The flame retardant resistance of this based composition is based on the synergistic function between these three kinds of components, and they are taking place to cause forming a kind of tangible and firm char layer under the incendiary situation, and its protection polymkeric substance avoids further burning.Mixture based on this based composition shows excellent flame-retardant performance usually, for example shows such performance in according to limited oxygen index (LOI) test method of ISO 4589-A-IV.Tape armored cable and bigger pipeline (not armouring) cable also must satisfy specific wireline test requirement, for example the combustion test of the single electric wire that carries out according to IEC 332-1.But pipeline electric wire great majority are little, and are difficult to reach IEC 332-1 standard based on the electric wire less than 4 square millimeters of this based composition.Therefore, the flame retardant resistance of this based composition still can be improved.
Therefore, one of purpose of the present invention is, a kind of flame retardant compositions is provided, and it has kept good mechanical properties, particularly fine balance snappiness and inflexible has improved flame retardant properties simultaneously.
The present invention is based on following discovery: can realize this goal of the invention by a kind of polymer composition, said composition also contains a kind of inorganic filler particle except a kind of alkene homopolymerization and/or multipolymer, at least a portion size is less than 1 micron, preferably less than 0.7 micron in this particle.
Therefore, the invention provides a kind of flame retardant compositions, it comprises
(A) account for a kind of alkene homopolymerization and/or the multipolymer of whole polymer composition 30 to 70 weight %,
(B) a kind of compound that contains silicone base,
(C) account for a kind of mineral filler of whole polymer composition at least 10 weight %,
Wherein the size-grade distribution of component (C) makes that at least 10 weight % of whole polymer compositions are sizes less than 0.7 micron particle.
The present composition has passed through single electric wire combustion testing and has shown improved dropping down property owing to it, thereby demonstrates the flame retardant resistance than prior art material improvement.In addition, to go out hazardous property littler and do not have corrosive gas for this composition certain slowly-releasing when decomposing.
The purpose of test method IEC 332-1 is definite obstruction that single upright cable fire is spread.Cable (600 millimeters) is installed by vertically orient, and this cable sample is applied the flame of 1kW with miter angle from 475 millimeters places far away of cable upper bracket, and this flame is produced by propane gas torch.Distance between the last lower bracket should be 550 millimeters.For the cable of external diameter, applied flame 60 seconds less than 25 millimeters.In order to carry out this test, after propane gas torch was removed, flame should extinguish, and in downward 50 millimeters of ceiling hold and should observe below 540 millimeters and do not burn.
In the composition of the present invention, the composition of olefin polymer (A) and select can be different, this depends on the present composition whether as one deck of electric wire or cable, and depends on for which kind of purpose and use this layer.Certainly, olefin polymer (A) also can comprise a kind of different alkene mixture of polymers.
Component (A) by alkene, preferably homopolymerization and/or the multipolymer by ethene forms.It for example comprises, the homopolymer of ethene, propylene and butylene or multipolymer, and the polymkeric substance of divinyl or isoprene.Suitable Alathon and multipolymer comprise: new LDPE (film grade), linea low density, middle density or high density polyethylene(HDPE) and ultra-low density polyethylene.Suitable ethylene copolymer comprises: have C
3-to C
20-alhpa olefin, C
1-to C
6-alkyl acrylate, C
1-to C
6-those ethylene copolymers of alkyl methacrylate, vinylformic acid, methacrylic acid and vinyl acetate.The preferred embodiment of alkyl-alpha alkene is propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.
But can also use the polymkeric substance of crosslinked with silicane, promptly, use has the polymkeric substance of the unsaturated silane monomer preparation of hydrolysable group, and these hydrolysable group can pass through hydrolytic crosslinking and condensation formation silanol in the presence of water and optionally a kind of silanol condensation catalyst.
In the preferred embodiment of the present composition, component (A) further comprises, and preferably is grouped into a kind of olefin copolymer, preferred a kind of polar olefin copolymer by following one-tenth.
With polar group be defined as will be functionalized group, it comprises at least a element outside carbon and the hydrogen.
Polar copolymer is preferably a kind of olefin/propylene acid esters further, optimal ethylene/acrylate, and/or alkene/acetic ester, the multipolymer of optimal ethylene/acetic ester.
Further preferred, this polar copolymer comprises the multipolymer of alkene optimal ethylene and one or more comonomers, and comonomer is selected from C
1-to C
6-alkyl acrylate, C
1-to C
6-alkyl methacrylate, vinylformic acid, methacrylic acid and vinyl acetate.This multipolymer also can contain ionomeric structure (resembling in the Surlyn type polymkeric substance that is present in DuPont for example).
Further preferred, this polar polymer comprises a kind of by ethene and C
1-to C
4The multipolymer that-alkyl (for example methyl, ethyl, propyl group or butyl), acrylate or vinyl-acetic ester form.
Particularly preferably be, this polar polymer comprises the multipolymer of a kind of alkene optimal ethylene and a kind of acrylic copolymer, for example ethylene acrylic acid co polymer and ethylene methacrylic acid copolymer.
These multipolymers also can contain other monomer except the comonomer of ethene and defined.For example, can use terpolymer, it is between esters of acrylic acid and the acrylic or methacrylic acid, perhaps esters of acrylic acid and vinyl silanes, or esters of acrylic acid and siloxanes, the perhaps terpolymer of vinylformic acid and siloxanes.
This polar copolymer can for example the monomer and the polar comonomer of alkene carry out the copolyreaction manufacturing by polymkeric substance, but also can be a kind of graftomer, for example a kind of polyolefine, wherein one or more comonomers are grafted on this main polymer chain for example acrylic acid-grafted polyethylene.
Further preferably, in the component (A) of per 100 weight parts (pbw), this polar polymer accounts for 30 weight parts (pbw) or more, more preferably accounts for 50 weight parts or more, and more preferably 70 weight parts or more.Most preferred composition (A) is made of this polar polymer fully.
In this composition, the content of polymeric constituent (A) is 30 to 70 weight % of whole compositions, preferred 40 to 60 weight %.
Fire-retardant combination of the present invention further contains a kind of compound (B) of siliceous ketone groups.
In a preferred embodiment of composition of the present invention, component (B) is a kind of silicone fluid or colloid (gum), or a kind of multipolymer of alkene optimal ethylene, this multipolymer comprises the comonomer of at least a siliceous ketone groups, perhaps a kind of mixture of any these compounds.Described comonomer is vinyl polyoxy silane preferably, for example vinyl unsaturated polyester dialkyl siloxane (polybishydrocarbylsiloxane).
Applicable to silicone fluid of the present invention and colloid is known, and comprises for example organopolysiloxane polymer, and it comprises and is selected from R
3SiO
0.5, R
2SiO, R
1SiO
1.5, R
1R
2SiO
0.5, RR
1SiO, R
1 2SiO, RSiO
1.5And SiO
2Chemically combined silicon alkoxyl group (siloxy) unit of unit and composition thereof, wherein each R represents a saturated or undersaturated monovalence alkyl independently, and each R
1Represent a base as R, perhaps one is selected from hydrogen, hydroxyl, alkoxyl group, aryl, vinyl or allylic group.
This organopolysiloxane preferred number average molecular weight Mn is about 10 to 10000000.Carry out the mensuration of molecular weight distribution (MWD) with GPC.Use CHCl
3As solvent.Use Shodex-Mikrostyragel (10
5, 10
4, 10
3, 100 ) the post group, RI-detector and a NMWD polystyrene are demarcated.These GPC tests are at room temperature carried out.
Silicone fluid or colloid can contain that gas-like phase white carbon black (fumed silica) filler that is generally used for making the silicone rubber hardening of for example maximum 50 weight %.
Alkene, the multipolymer of the comonomer of optimal ethylene and at least a siliceous ketone groups are a kind of vinyl unsaturated polyester dialkyl siloxanes suc as formula (I):
N=1 to 1000 wherein, and
R and R ' are vinyl, branching or nonbranched alkyl independently, and this alkyl has 1 to 10 carbon atom; The aryl of 6 to 10 carbon atoms; The alkaryl of 7 to 10 carbon atoms; The perhaps aralkyl of 7 to 10 carbon atoms.
This compounds is for example open in WO 98/12253, and its content is incorporated the present invention into through quoting.
Preferably, component (B) is a polydimethylsiloxane, and preferred Mn is about 1000 to 1000000, more preferably 200000 to 400000, and/or the multipolymer of a kind of ethene and vinyldimethicone.Preferred these components (B) are that it is the commercial goods.
The term that uses among the application " multipolymer " means and comprises, produce by copolyreaction or by with the monomer-grafted multipolymer that produces to the main polymer chain.
In the composition, the content of the compound of preferred siliceous ketone groups (B) is 0.5 to 40% of composition total weight, more preferably 0.5 to 10%, and more more preferably 1 to 5%.
In addition, the addition of the compound of preferred siliceous ketone groups makes the silicone group all account for 1 to 20 weight % in the composition, more preferably 1 to 10 weight %.
The size-grade distribution of mineral filler component (C) makes at least 10 weight % of whole polymer compositions, and more preferably at least 15% is lower than 0.7 micron particle for size.
Preferably, the size-grade distribution of component (C) makes at least 10 weight % of whole compositions, and more preferably at least 15 weight % are of a size of 0.65 micron or littler, more preferably 0.60 micron or littler, and most preferably be lower than 0.5 micron particle.
More preferably, the size-grade distribution of component (C) makes maximum 55 weight % of whole polymer compositions, more preferably maximum 45 weight %, more preferably maximum again 30 weight % are that size is lower than 0.7 micron, more preferably 0.65 micron or littler, more preferably 0.60 micron or littler and most preferably be lower than 0.5 micron particle again.
Further preferred, the size-grade distribution of component (C) makes its size of particle of at least 50 weight % be lower than 0.7 micron, more preferably 0.65 micron or littler, and more preferably 0.60 micron or littler again, and most preferably be lower than 0.5 micron.
In addition, the granularity of at least 60 weight % is 1 micron or littler in the preferred ingredient (C), and more preferably the particle size of at least 70 weight % is 1.5 microns or littler, and more more preferably the particulate of at least 80 weight % be of a size of 2 microns or littler.
Using length-to-diameter ratio is not that length-to-diameter ratio is the ratio between the wealthyest size of particulate and the shortest size under 1 the inorganic filler particle situation, and particle size is defined as the wealthyest size of particle and the digital averaging of short size.
Preferably, mineral filler (C) comprises at least one class filler, the length-to-diameter ratio of inorganic filler particle wherein, and promptly the ratio between the wealthyest size of particle and the shortest size is lower than 5.
For example, CaCO
3The common length-to-diameter ratio of particle for example is 1 to 2 near 1.
Only use a class mineral filler, perhaps use two classes or the mixture of multiclass mineral filler more, make all filler particles length-to-diameter ratios identical, this within the scope of the present invention.
Therefore, mineral filler (C) can be fully be lower than 5 filler by the particle length-to-diameter ratio and forms.
In a preferred embodiment, mineral filler (C) comprises the formed mixture of a kind of at least two class fillers, and a class particulate length-to-diameter ratio is lower than 5, and a class particulate length-to-diameter ratio is 5 or higher.
For example, the particle length-to-diameter ratio of fiber is generally 10 and Geng Gao, and the strip filler for example particle length-to-diameter ratio of mica, aluminium hydroxide and graphite is generally 5 to 100.
The content of mineral filler in the preferred composition (C) is higher than 10 weight %, more preferably 30 weight % or higher, more preferably 32 weight % or higher again, more preferably 34 weight % or higher again, and 35 weight % or higher most preferably.
The more preferably maximum 70 weight % of the content of mineral filler in the composition (C), more preferably maximum 60 weight % and most preferably maximum 55 weight %.
Component (C) is applicable to that promptly the mineral filler material of the present composition comprises all filler materials well known in the prior art.Component (C) also can comprise the mixture of any this class filler.The example of this class filler material is: the oxide compound of aluminium, magnesium, calcium and/or barium, oxyhydroxide and carbonate.
Preferred ingredient (C) comprises 1 to 13 family in a kind of " periodic table of elements ", more preferably 1 to 3 family, more preferably 1 family and 2 families again, and the mineral compound of 2 family's metals most preferably.
When using among the present invention, the numbering of chemical group is according to the IUPAC system, and wherein the group in the period of element system is numbered 1 to 18.
Preferably, mineral filler component (C) comprises a kind of compound, and it is neither oxyhydroxide, neither hydrate, more preferably comprise a kind of compound that is selected from carbonate, oxide compound and vitriol, and most preferably comprise a kind of carbonate.
The preferred embodiment of these compounds is lime carbonate, magnesium oxide and huntite Mg
3Ca (CO
3)
4, particularly preferred example is a lime carbonate.
Though mineral filler (C) preferably is not an oxyhydroxide, it can contain a spot of oxyhydroxide, generally is less than 5% of filler weight, preferably is less than 3% weight.For example, may there be a spot of magnesium hydroxide in the magnesium oxide.And although filler (C) is not a hydrate, it can contain a spot of water, is less than 3% of filler weight usually, preferably is less than 1 weight %.But most preferred composition (C) does not contain oxyhydroxide and/or water fully.
Preferably, the component of flame retardant compositions of the present invention (C) contains 50 weight % or more lime carbonate, and more preferably it is made of lime carbonate basically fully.
Mineral filler can comprise a kind of filler, and it has carried out surface treatment with a kind of organosilane, a kind of polymkeric substance, a kind of carboxylic acid or salt etc., to help processing and better fillers dispersed is provided in this organic polymer.This coating accounts for the 3 weight % that are no more than of filler usually.
Preferably, these compositions of the present invention contain organic metal salt or the polymeric coating that is less than 3 weight %.
Except above-mentioned component (A), (B) with (C), composition of the present invention can contain a spot of other composition, for example as an example, and antioxidant and or ultra-violet stabilizer.
And, also available other mineral filler for example glass fibre as the part of this composition.
Composition of the present invention can be crosslinkable.What know is, adopt irradiation or as the linking agent of organic superoxide make thermoplastic polymer composition crosslinked, thereby composition of the present invention can contain a kind of linking agent of convention amount.Silane-crosslinkable polymer may contain a kind of silanol condensation catalyst.
Can prepare flame retardant compositions of the present invention by the following method,
A) prepare a kind of masterbatch, this masterbatch comprises compound, additive and the polymkeric substance of siliceous ketone groups, and is then compound with mineral filler and matrix polymer, perhaps
B) compound all components of a step.
In order to mix, can use conventional compound or blending equipment, for example Banbury, two roller mill, Bu Si (buss) are total to kneading machine, perhaps twin screw extruder.Preferably, preparing this composition is at a certain temperature with their blend together, and this temperature height must be enough to softening and plasticized polymer, and typical temperature is in 120 to 200 ℃ scope.
Fire-retardant combination of the present invention can be used in diversified purposes and the product.Can be for example with this composition molding, extrude or alternate manner is processed into: moulded parts, sheet material, reticulation and fiber.
As above-mentioned already mentioned, the preferable use of fire-retardant combination of the present invention is to be used to make wire conduit, plug, electric wire or cable, perhaps is used for injection moulding, and particularly preferred purposes is to make electric wire or cable.This composition can be extruded around electric wire or cable,, perhaps be can be used as bottom mixture (bedding compound) so that form a kind of insulation layer or jacket layer.
Further illustrate the present invention below by way of embodiments and drawings:
Fig. 1 shows the inorganic CaCO that is used for each embodiment
3The size-grade distribution of filler.
Embodiment:
1. composition is compound
Make of the present inventionly and be used for correlated flame retardant compositions, method is in 180 ℃ of temperature component to be combined with each other in a bench roller press.
2. the composition of manufacturing and used material
In order to make Comparative composition and composition of the present invention, use following raw material:
The EMAA=ethylene methacrylic acid copolymer, it contains the methacrylic acid of 9 weight %, at 190 ℃, 2.16kg (MRF
2) melt flow be 3.0 grams/10 minutes, and density is 0.934 gram/cubic centimetre;
The EAA=ethylene acrylic acid co polymer, it contains the vinylformic acid of 9 weight %, MRF
2Be 8 grams/10 minutes, and density is 0.936 gram/cubic centimetre;
EBA=ethylene butyl acrylate multipolymer, it contains the butyl acrylate of 8 weight %, and MFR
2Be 0.4 gram/10 minutes;
Silicone (m.b.)=Masterbatch (masterbatch) contains 40% polydimethyl silicone elastomer and 60% new LDPE (film grade),
CaCO
3(0.4)=mean particle size (d
50Value) be 0.4 micron precipitated chalk,
CaCO
3(0.65)=mean particle size (d
50Value) be 0.65 micron grinding calcium carbonate,
CaCO
3(1.4)=mean particle size (d
50Value) be 1.4 microns grinding calcium carbonate,
Stablizer=Irganox 1010 (phenol antioxidant).
Compound as above-mentioned these compositions that make, the consumption of component is shown in the table 1 with weight %.
3. the production of cable
With the 0.7+ of the different compositions of general introduction in the table 1/-the 0.1mm isolator is being expressed on the laboratory extruding production line (160-170-180 ℃, rpm, pressure die) on 1.5 square millimeters the copper conductor.
4. test method
A) under 190 ℃ and 2.16 kilograms of weight, measure the melt flow rate (MFR) MFR of composition according to ISO 1133
2
B) complete combustion test of carrying out single electric wire according to IEC 332-1.In order to satisfy this test, after the flame of 1kW propane gas torch was removed, flame should extinguish, and in downward 50 millimeters of ceiling hold and should observe below 540 millimeters and do not burn.The electric wire that reaches this standard is designated as " qualified " in table 1, otherwise is designated as " defective ".
C) measure these droplets of material in the following manner and drop down tendency:
60 * 60 * 3 millimeters patch to this material is exerted pressure, and to be placed on mesh size be on 12 the steelframe.With the Bunsen burner (Bunsen burner) of 1kW (950+/-50 ℃) from the below with 45 by steelframe this patch that burns, oneself extinguish (patch is by perfect combustion) up to fire.In the drippage entry that calcination goes out.Filter these residues in the water outlet, drying is also weighed.Drip drop down trend be the residue collected in the water divided by the initial weight of patch, multiply by 100.That is, drop down the percentage ratio that accounts for original sample weight of loss owing to dripping.Present method is based on French method NF P 92-505.
D) measure size-grade distribution and mean particle size (d with Sedigraph 5100
50Value).This sedimentation method is that different size particulate gravity induces the measurement of travel rate to determine granularity in the known liquid of through performance.The speed that particle falls in liquid is described with Stoke's law.Maximum particle descends the fastest, and minimum particle descends the slowest, up to all particles make a decision and liquid limpid till.Because different particles shows as consistent shape hardly, thus each granularity as a kind of " equivalent spherical diameter " record, it is the diameter with same material ball of identical gravity speed.
Use the thin collimated beam of a branch of low energy X ray to measure subsidence rate, this light beam arrives detector by sample pool.Because the particle in this pond absorbs X ray, so only be the initial X ray light beam arrival detector of certain percentage.This is the raw data that is used for determining containing the pond size-grade distribution of sedimentation liquid.
X-ray source and detector are kept static installation, and sample pool vertical shifting between them.Because the disruptive features of light beam, guaranteed the automatic location of sample pool, eliminated other system since their installation move with uncertainty.Sample pool contains a transparent window, by this window, from the X ray arrival detector of light source.The granular mass distribution influence at difference place arrives the X ray umber of pulse of detector in the sample pool.This X ray pulse counting be used to derive the size-grade distribution and the percentage quality of given particle diameter.The material that mean particle size is defined as 50 weight % is the granularity during than this coarse size than the material of this fine size and 50 weight %.
5. result
Performance comparison between (embodiment's 1 to the 11) present composition of listing in the table 1 and (Comparative Examples 1 to 3) Comparative composition shows that its single electric wire combustion test of cable that the present composition is made is qualified, thereby has improved flame retardant resistance.
Table 1:
| (weight %) | | | | | | | Embodiment 7 |
| EMAA(％) | - | - | - | - | - | - | 52.3 |
| EAA | 52.3 | 52.3 | 57.3 | - | - | - | - |
| EBA | - | - | - | 42.3 | 47.3 | 52.3 | - |
| Silicone (m.b.) | 12.5 | 12.5 | 12.5 | 12.5 | 12.5 | 12.5 | 12.5 |
| CaCO 3(0.4) | - | - | 30 | 45 | 40 | 35 | - |
| CaCO 3(0.65) | 35 | 35 | - | - | - | - | 35 |
| CaCO 3(1.4) | - | - | - | - | - | - | - |
| Stablizer | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| IEC 332-1 | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| (weight %) | Embodiment 8 | Embodiment 9 | | Embodiment 11 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| EMAA(％) | 57.3 | 52.3 | 47.3 | 42.3 | - | - | - |
| EAA | - | - | - | - | 42.3 | 52.3 | - |
| EBA | - | - | - | - | - | - | 52.3 |
| Silicone (m.b.) | 12.5 | 12.5 | 12.5 | 12.5 | 12.5 | 12.5 | 12.5 |
| CaCO 3(0.4) | 30 | 35 | - | - | - | - | - |
| CaCO 3(0.65) | - | - | 40 | 45 | - | - | - |
| CaCO 3(1.4) | - | - | - | - | 45 | 35 | 35 |
| Stablizer | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| IEC 332-1 | Qualified | Qualified | Qualified | Qualified | Defective | Defective | Defective |
In addition, result displayed shows in the table 2, and the present composition has dripping of improvement and drops down tendency.The mixture that is tried all contains the silicone (m.b.) of 12.5 weight %, the stablizer of 0.2 weight %, CaCO
3Quality and quantity represented as table 2, and surplus is EBA.
Table 2:
| Mean | 30％CaCO 3 | 35 | 40％CaCO 3 |
| 0.4 micron | 12 | 9 | 2 |
| 0.65 micron | 8 | 1 | 2 |
| 1.4 micron | 33 | 8 | 12 |
Claims (13)
1. fire-retardant polymer composition, it comprises:
(A) account for a kind of alkene homopolymerization and/or the multipolymer of whole polymer composition 30 to 70 weight %,
(B) a kind of compound that contains silicone base,
(C) account for a kind of mineral filler of whole polymer composition at least 10 weight %,
Wherein the size-grade distribution of component (C) makes that at least 10 weight % of whole polymer compositions are size less than 0.7 micron particle.
2. the composition of claim 1, wherein the size-grade distribution of component (C) makes that at least 10 weight % of whole polymer compositions are that size equals 0.65 micron or less than 0.65 micron particle.
3. each composition of aforementioned claim, wherein the size-grade distribution of component (C) makes that at least 10 weight % of whole polymer compositions are that size equals 0.5 micron or less than 0.5 micron particle.
4. each composition of aforementioned claim, the total amount of wherein mineral filler (C) is 30 to 55 weight % of whole polymer compositions.
5. each composition of aforementioned claim, wherein mineral filler (C) neither hydrates neither oxyhydroxide.
6. each composition of aforementioned claim, wherein mineral filler (C) comprises carbonate, oxide compound and/or the vitriol of the element of 1 to 13 family in the periodic table of elements.
7. each composition of aforementioned claim, wherein component (C) comprises a kind of mineral compound, and its particle has and is lower than 5 length-to-diameter ratio.
8. each composition of aforementioned claim, wherein polymkeric substance (A) comprises a kind of polar olefin copolymer.
9. the composition of claim 8, wherein polymkeric substance (A) comprises a kind of multipolymer, and this multipolymer is the multipolymer of a kind of acrylic comonomers and a kind of alkene.
10. each composition of aforementioned claim, wherein the compound of siliceous ketone groups (B) is a kind of silicone fluid and/or colloid, and/or a kind of olefin copolymer, this multipolymer comprises a kind of comonomer of siliceous ketone groups.
11. each composition of aforementioned claim, wherein all the silicone base mass contg in the compositions is 1 to 20 weight % of whole compositions.
12. each composition of aforementioned claim is used for wire conduit, plug, electric wire or cable, perhaps is used for injection moulding, is preferred for electric wire or cable.
13. electric wire or cable, its one deck that has contain each composition of claim 1 to 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03019364.3 | 2003-08-27 | ||
| EP03019364A EP1512719B1 (en) | 2003-08-27 | 2003-08-27 | Flame retardant polymer composition comprising fine particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1842572A true CN1842572A (en) | 2006-10-04 |
Family
ID=34130081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800244316A Pending CN1842572A (en) | 2003-08-27 | 2004-08-25 | Flame retardant polymer composition comprising fine particles |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20070112111A1 (en) |
| EP (1) | EP1512719B1 (en) |
| JP (1) | JP2007503493A (en) |
| CN (1) | CN1842572A (en) |
| AT (1) | ATE410475T1 (en) |
| AU (1) | AU2004268042B2 (en) |
| CA (1) | CA2536589A1 (en) |
| DE (1) | DE60323974D1 (en) |
| EA (1) | EA008923B1 (en) |
| ES (1) | ES2315448T3 (en) |
| PL (1) | PL379224A1 (en) |
| WO (1) | WO2005021642A1 (en) |
Cited By (4)
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| CN102056979A (en) * | 2008-06-05 | 2011-05-11 | 博里利斯股份公司 | Flame retardant polyolefin composition comprising a high amount of inorganic filler |
| CN102916279A (en) * | 2011-08-04 | 2013-02-06 | 巴斯威尔股份有限公司 | Power transmission bus filler material and application thereof |
| CN104302694A (en) * | 2012-04-27 | 2015-01-21 | 博里利斯股份公司 | Flame retardant polymer composition |
| CN104755559A (en) * | 2012-12-27 | 2015-07-01 | 株式会社藤仓 | Flame-retardant resin composition and cable using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006321934A (en) * | 2005-05-20 | 2006-11-30 | Sunallomer Ltd | Fire retardant thermoplastic resin composition and its molded article and electric wire |
| ATE443336T1 (en) * | 2006-05-31 | 2009-10-15 | Borealis Tech Oy | FIRE-RESISTANT POLYMER COMPOSITION CONTAINING BROAD MOLECULAR WEIGHT DISTRIBUTION POLYOLEFINS |
| EP2150385B8 (en) | 2007-06-03 | 2012-03-21 | Imerys Pigments, Inc. | Spunlaid fibers comprising coated calcium carbonate, processes for their production, and nonwoven products |
| JP2010111760A (en) * | 2008-11-06 | 2010-05-20 | Hitachi Cable Ltd | Non-halogen resin composition, non-halogen insulated electrical wire, and non-halogen cable |
| AU2010217302A1 (en) * | 2009-02-25 | 2011-08-11 | Nexans | A fire performance material, and cable including the material |
| KR102399144B1 (en) | 2014-03-04 | 2022-05-19 | 다우 실리콘즈 코포레이션 | Thermoplastic polymer masterbatch |
| EP3401929A1 (en) | 2017-05-09 | 2018-11-14 | Borealis AG | Cable insulation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0319924B1 (en) * | 1987-12-08 | 1995-11-22 | Idemitsu Petrochemical Company Limited | Process for producing thermoplastic resin composition |
| JPH02255843A (en) * | 1988-11-22 | 1990-10-16 | Furukawa Electric Co Ltd:The | Flame-retarding resin composition and flame-retarding cable prepared by using same |
| US5091453A (en) * | 1989-04-21 | 1992-02-25 | Bp Chemicals Limited | Flame retardant polymer composition |
| JPH0512928A (en) * | 1991-07-03 | 1993-01-22 | Hitachi Cable Ltd | Flame resisting electrical insulating material |
| KR100253955B1 (en) * | 1992-06-09 | 2000-04-15 | 후루타 다케시 | Polyolefin resin composition, process for the preparation thereof and molded article made thereof |
| JP3372298B2 (en) * | 1993-06-10 | 2003-01-27 | 鐘淵化学工業株式会社 | Modified polyolefin resin composition and polyolefin resin composition containing the same |
| CN1152471A (en) * | 1995-11-10 | 1997-06-25 | 阿尔卡塔尔-阿尔斯托姆通用电气公司 | Composition with high anti-fire-spreading property |
| EP0774488A1 (en) * | 1995-11-11 | 1997-05-21 | Alcatel | Fire propagation inhibiting composition |
| SE507330C2 (en) * | 1996-09-17 | 1998-05-11 | Borealis As | Flame retardant composition and cable comprising the flame retardant composition |
| JP3735444B2 (en) * | 1997-04-09 | 2006-01-18 | 日本ユニカー株式会社 | Flame retardant resin composition |
| JPH10334737A (en) * | 1997-05-30 | 1998-12-18 | Hitachi Cable Ltd | Wire/cable covered with elastomer containing fluorine |
| US6077892A (en) * | 1998-09-04 | 2000-06-20 | Dow Corning Corporation | Curable polyolefin compositions containing organosilicon compounds as adhesion additives |
| JP4778601B2 (en) * | 2000-03-27 | 2011-09-21 | 出光興産株式会社 | Flame retardant polycarbonate resin composition and molded article |
| AU783561B2 (en) * | 2001-03-28 | 2005-11-10 | Oji Paper Co. Ltd. | Coated paper sheet |
| EP1316581A1 (en) * | 2001-11-28 | 2003-06-04 | Borealis Technology Oy | Flame retardant polymer composition |
| EP1396865A1 (en) * | 2002-09-03 | 2004-03-10 | Borealis Technology Oy | Flame retardant polymer composition |
-
2003
- 2003-08-27 AT AT03019364T patent/ATE410475T1/en not_active IP Right Cessation
- 2003-08-27 EP EP03019364A patent/EP1512719B1/en not_active Expired - Lifetime
- 2003-08-27 DE DE60323974T patent/DE60323974D1/en not_active Expired - Lifetime
- 2003-08-27 ES ES03019364T patent/ES2315448T3/en not_active Expired - Lifetime
-
2004
- 2004-08-25 US US10/569,334 patent/US20070112111A1/en not_active Abandoned
- 2004-08-25 EA EA200600463A patent/EA008923B1/en not_active IP Right Cessation
- 2004-08-25 CA CA002536589A patent/CA2536589A1/en not_active Abandoned
- 2004-08-25 JP JP2006524324A patent/JP2007503493A/en active Pending
- 2004-08-25 AU AU2004268042A patent/AU2004268042B2/en not_active Expired - Fee Related
- 2004-08-25 CN CNA2004800244316A patent/CN1842572A/en active Pending
- 2004-08-25 WO PCT/EP2004/009491 patent/WO2005021642A1/en active Application Filing
- 2004-08-25 PL PL379224A patent/PL379224A1/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056979A (en) * | 2008-06-05 | 2011-05-11 | 博里利斯股份公司 | Flame retardant polyolefin composition comprising a high amount of inorganic filler |
| CN102056979B (en) * | 2008-06-05 | 2014-04-30 | 博里利斯股份公司 | Flame retardant polyolefin composition comprising a high amount of inorganic filler |
| CN102916279A (en) * | 2011-08-04 | 2013-02-06 | 巴斯威尔股份有限公司 | Power transmission bus filler material and application thereof |
| CN102916279B (en) * | 2011-08-04 | 2016-01-27 | 巴斯威尔股份有限公司 | Electric power transfer bus packing material and application thereof |
| CN104302694A (en) * | 2012-04-27 | 2015-01-21 | 博里利斯股份公司 | Flame retardant polymer composition |
| CN104302694B (en) * | 2012-04-27 | 2016-06-29 | 博里利斯股份公司 | Flame retardant compositions |
| CN104755559A (en) * | 2012-12-27 | 2015-07-01 | 株式会社藤仓 | Flame-retardant resin composition and cable using same |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE410475T1 (en) | 2008-10-15 |
| EA200600463A1 (en) | 2006-08-25 |
| AU2004268042B2 (en) | 2009-06-04 |
| WO2005021642A1 (en) | 2005-03-10 |
| AU2004268042A1 (en) | 2005-03-10 |
| ES2315448T3 (en) | 2009-04-01 |
| CA2536589A1 (en) | 2005-03-10 |
| DE60323974D1 (en) | 2008-11-20 |
| JP2007503493A (en) | 2007-02-22 |
| EP1512719A1 (en) | 2005-03-09 |
| EP1512719B1 (en) | 2008-10-08 |
| EA008923B1 (en) | 2007-08-31 |
| PL379224A1 (en) | 2006-08-07 |
| US20070112111A1 (en) | 2007-05-17 |
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